Composition of matter



?atented dan g, 19%5 rattan @OMPUSETIQN @F MATTER iii-land M. Reid, Woodbury, N. 3., assignor to Socony-Vacuum Oil Company, Incorporated, a corporation of New York No Drawing. Original application April 10, 1946,

Serial No. 328,873. Divided and this applicationflugust 5, 1942, Serial No. 453,725

11 Claims.

This invention has to do with new chemical compounds or reaction products which maybe generally designated as the metal salts of alkylated hydroxyaromatic sulfides or as the sulfides of alkyl-substituted aryl metal oxides or hydroxylates. Although the invention is broadly concerned with chemical compounds or compositions coming within the above-designated general classification, it contemplates as a preferred group coming within such general classification those compounds or condensation products which are soluble or miscible with mineral oil.

My invention is predicated upon the discovery that the oil-miscible compounds or condensation products contemplated herein when blended with a viscous mineral oil fraction, such as a hydrocarbon lubricating oil, will improve the oil in various respects. For example, I have found that the compounds or reaction products contemplated herein will inhibit oxidation of the oil, thereby retarding the formation of sludge and acidic products. They also have a peptizing action on such sludge as may be present or as may eventually be formed. Thus, any one of these preferred oil-miscible compounds or condensation products may, for example, be used in internal combustion engine lubricants to retard or prevent the sticking of piston rings, the clogging of piston ring slots, the corrosion of bearings and other parts susceptible to attack by acidic products of oxidation in the oil, and through a proper choice of metal. substituent (lead, copper, tin, or zinc, for example) the load-carrying ability or lubricity of the oil may be improved.

The alkyl substituents on the aryl nuclei of the compounds or condensation products contemplated herein act to impart oil-miscibility to the product and for the preferred general class of oil-miscible compounds these alkyl substituents should =contain at least carbon atoms. Within this preferred general class of oil-miscible compounds special preference is given to compounds wherein the alkyl substituents. contain at least twenty carbon atoms. This especially-preferred sub-group of compounds having the so-called heavy alkyl groups oi at least twenty carbon atoms (such as are derived, for example, from Friedel-Craits condensation with chlorinated parafiin wax) act to improve the oil in the same respects noted above, and in addition they improve the viscosity index and pour point of the oil.

It is to be understood that the present inven tion is not concerned with mineral oil compositmns, such compositions forming the subject matter of my copending application Serial No. 328,873, filed April 10, 1940, (which in turn is a continuation-in-part of my application Serial No. 222,755, filed August 3, 1938, and now issued as Patent No. 2,197,835), of which the present application is a division and to which reference is made for further details in the compositionof these compounds or reaction products.

It is also to be understood that the present invention is not confined to the oil-miscible or oil-soluble compounds and that the use oi the preferred oil-miscible compounds is not confined to the improvement of mineral oils, since this whole class of new materials is possessed of valuable properties irrespective of oil-miscibility. For example, the compounds or condensation products contemplated herein may be used as intermediaries in the production of resins, resin-like materials, rubber substitutes,.etc. Certain of the compounds or compositions are possessed of valuable pharmaceutical, insecticidaLor similar properties, such, for example, as those derived from the presence of a particular metal or metaloxy group. Numerous other uses and applications of the compounds orcondensation products contemplated herein will be readily apparent to those skilled in the art from the following description oi their compositions and a typical method for synthesizing them. I

As aforesaid, the compounds or condensation products contemplated herein may be broadly designated as the sulfides of alkyl-substituted aryl metal oxides or hydroxylates. Thus, they may be considered as the sulfides (thio ethers and polysulfides) of the alkyl-substituted aryl metal hydroxylates disclosed and claimed in Patent No. 2,252,663, issued to me on August 12, 1941, which are obtained by condensation with a sulfur halide as disclosed in the parent application Serial No. 222,755 hereinabove referred to. Thus, a typical compound or condensation product of the type contemplated herein may be represented by the general formula I MO OM droxyaromatic (phenol) sulfide. It will be observed that this compound is a condensation which this is a division.

In general it appears that any metal may be employed as the metal M in compounds or condensation products of the aforesaid type to provide valuable oil addition agents. The metals contemplated herein may be broadly classified as metals of groups I to VlII, inclusive, of the periodic system. These metals comprise the following: the alkali metals: lithium, sodium, potassium, rubidium, and caesium; the alkaline earth group: beryllium, magnesium, calcium, strontium, and barium; the metals zinc, cadmium, mercury, scandium; the metals aluminum, gallium, indium, thallium, titanium, zirconiuni cerium,

to a Friedel-Crafts condensation reaction with a halogenated aliphatic hydrocarbon, which for obtaining the preferred multifunctional addition agents should be an aliphatic hydrocarbon containing at least twenty carbon atoms or a mixture of aliphatic compounds predominantly comprised of compounds having at least'twenty carbon atoms. This alky'lation may also be carried out with unsaturated hydrocarbons or aliphatic alcohols, using H2504 or anhydrous aluminum chloride as a catalyst. In alkylating phenols with high molecular weight alcohols, however, it is preferred to convert the alcohol to the corresponding halide (or polyhalide) and then condense the alkyl halide with the hydroxyaromatic compound by the Friedel-Crafts reaction. For obtaining the preferred multifunctional addition agent with unsaturated hydrocarbons or aliphatic alcohols they should be high molecular Weight compounds containing at least twenty carbon atoms, such, for example, as eicosylene, cerotene, melene, polymerized isobutylene, etc., and myricyl alcohol, ceryl alcohol, etc.

The Friedel-Crafts synthesis is preferred for' obtaining the alkylated hydroxyaromatic compound, and as a source of the alkyl substituent preference is given to mixed high molecular weight hydrocarbons typified by those which thorium; germanium, tin, and lead; vanadium,

columbium, and tantalum; arsenic, antimony, and bismuth; chromium, molybdenum, tungsten, and uranium; rhenium, manganese, iron, cobalt, and nickel; ruthenium, rhodium, and palladium; osmium, iridium, and platinum.

Some of the rare earth metals are given in the foregoing. Other rare earth metals suitable for use in the metal oxide group of the sulfides of alkylated aryl metal oxides contemplated herein are those now commercially available as the cerium and yttrium group: namely, a mixture of V praseodymium, neodymium, samarium, europium,

gadolinium, terbium, dysprosium, holmium, erbium, thallium, and lutecium.

As aforesaid, the term sulfide, as used herein, is inclusive of the monosulfides, disulfides, trisulfides. tetrasulfides, etc.; that is, it includes both monosulfides and polysulfides andis also inelusive of such polymers and related complex derivatives as may be formed by the hereinafterdescribed procedures. The general procedure for synthesizing the sulfides of alkylated aryl metal oxi es is to first form the alkylated hydroxyaryl sulfide and then substitute the hydroxyl hydrogen with metal.

The alkylated hydroxyaryl sulfides can be prepared by the reaction of alkylated hydroxyaromatic compounds such as an alkyl-substituted phenol with sulfur or with sulfur halides. With sulfur dichloride, for example, the thio ether with the monosulfide linkage (11:1 in general Formula I) is formed, and with sulfur monochloride the disulfide linkage (11:2) is formed. By reaction with elementary sulfur, the main-products contain monosulfide linkages with HzS evolved in the condensation reaction. Sulfur condensation products or sulfides of higher sulfur content can be formed by (a) reaction of alkylated thio' phenols (aryl mercaptans) with sulfur monochloride or sulfur dichloride, and (b) reaction of a compound having a disulflde linkage with sulfur, or alkali polysulfides or alkyl tetrasulflde.

The alkylation of the hydroxyaromatic compound may be carried out in various ways. A preferred procedureis to subject a hydroxyaromatic compound or an oxyaromatic compound characterize the heavier products of petroleum, such as heavy petroleum oils of the lubricant type, petrolatumand crystalline petroleum wax or other compounds which will result in relatively long chain aliphatic substituents. Special preference is given to petroleum wax (paraffin wax) of melting point not substantially less than about 120 F., which is predominantly comprised of aliphatic hydrocarbons having a-molecular weight of at least350 and containing at least twenty carbon atoms.

Hydroxyaromatic compounds which may be used in the alkylation reaction are monoor poly-cyclic and monoor poly-hydric hydroxyaromatic compounds which may or may not be otherwise substituted. Specific examples of compounds 'which may be used in this reaction are: phenol, resorcinol, hydroquinone, catechol, cresol, xylenol, hydroxydiphenyl, benzylphenol, phenylethyl phenol, phenol resins, methyl hydroxydiphenyl, alpha and beta naphthol, xylyl naphthol,

benzyl phenol, anthranol, phenyl-methyl naphthol, phenanthrol, anisole, beta-naphthyl methyl ether, chlorphenol, and the like. Preference in general is to the monohydroxy phenols otherwise unsubstituted, particular preference being given to phenol and. alpha and betal naphthol. Mixed alkyl-aryl and aralkyl-aryl ethers such as anisole and beta-naphthyl methyl ether are given as examples because the Friedel-Crafts reaction with these ethers is accompanied by some rearrangement, yielding free hydroxyl groups.

Where it is desired to obtain a compound or condensation product in which the aryl nucleus contains in addition to, or instead of, residual hydrogen another substituent in addition to the oilsolubilizing alkyl group, it is pointed out that with the exception of substituents such as aralkyl,

aryl, alkaryl, halogen, hydroxyl, and aroxy, such substituent groups are introduced after alkyla tion of the hydroxyaromatic compound. The usual methods for the introduction of these substituents into non-alkylated hydroxyaromatic compounds may be employed in connection with the alkylated hydroxyaromatic compounds contemplated herein. Methods for the introduction of such substituents along with phenolic OM aseaera in a typical procedure for synthesizing these socalled wax substituted hydroxyaromatic compounds (wax-phenol) are described in my prior application Serial No. 206,683, now issued as Patent No. 2,197,833. Briefly, this procedure involves reacting a chlorinated wax such as chlorinated parafiin wax with a phenol in the presence of a Friedel-Crafts catalyst at elevated temperature. The chlorinated wax should have a chlorinecontent of from per cent to 16 per cent, and the reaction mixture may contain about three atomic proportions of chlorine (in a chlorwax of 16 per cent chlorine content) to one molecular proportion of phenol. A wax-pheno obtained from such a-reaction mixture may be designated as wax-phenol (3-16). Parenthetical expressions of the type (A-B) will be used hereinafter in connection with the wax-substituted derivatives to designate (A) the number of atomic proportions of chlorine in the chlorinated wax reacted with one mol of hydroxyaromatic compound and (B) the chlorine content of the chlorinated wax. In the above example A=3 and 3:16. The same designation will also apply to the sulfides of the wax-aryl metal oxides which constitute the ultimate product derived from the wax-phenol.

Illustrative procedures which may be followed in preparing the sulfides of alkyl-substituted hydroxyaromatic compounds and the sulfides of alkylated aryl metal oxides derived therefrom are given in the following examples, wherein the alkylated phenolf is preferably a wax-substituted phenol of the type last-described above for obtaining the wax-substituted derivatives which are especially preferred because of their I multifunctional oil-improving properties.

EXAMPLE ONE SYNTHESIS or ALKYLATED HYDROXYARYL SULFIDES A. Monosulfide linkage Reaction mixture PROCEDURE The alkylated phenol is dissolved in the solvent and brought to a. temperature of about 100 F., followed by addition of the sulfur halide. The

sulfur halide is introduced slowly, requiring about /2 hour for the addition, followed by refluxing the mixture about one hour to complete the reaction. HCl is evolved in the reaction, resulting 'finished product.

in fixation of sulfur in the aryl nucleus. After completion of the condensation reaction, the mixture is water-washed to remove the dissolved bydrochloricacid, followed by removal of diluents to give the finished product.

C. Trior tetra-sulfide linkage By reaction of the disulfide type of compound with elementary sulfur or alkali polysulfides or alkyl tetrasulfides, one or two atoms of sulfur can be added to the disulfide linkage, resulting in formation of the trior tetrasulfide derivative, respectively, The use of alkyl tetrasulfldes is preferred in this type of reaction.

- Reaction mixture Alkylated phenol disulfide mol The alkylated phenol disulfide, in solution in carbon disulfide, benzene, chlorbenzene, or ethylene dichloride, i brought to a temperature of about F. and treated with the ethyl tetrasulfide, followed by refluxing the mixture during a one-hour period to complete the addition of sulfur. The solvent is then distilled to give the EXAMPLE Two METAL DERIVATIVES or ALKYLATED HYnRoxYAizo- MATIC s-ULFIDES The metal oxides (phenates, naphtholates, etc.) of alkylated aromatic sulfides may be obtained and purified according to the same general procedures described in my prior application Serial No. 206,683 for synthesizing alkylated aryl metal oxides.

'In the formation of the alkali metal derivative, the alkylated phenol sulfide i reacted with an alcoholate of the desired alkali metal. formation of derivatives of other classes of metals, the preferred procedure consists in treating the alkylatd phenol sulfide with an equivalent of the salt of the desired metal in alcohol solution, followed by reaction with an equivalent amount of a sodium alcoholate, resulting in the formation of the alcoholate of the desired metal as the initial product. By heating the mixture to about 300 F. for a period of about one hour, the metal alcoholat'e is reacted with the hydroxyl group resulting in the formation of the metal phenate derivative. Normal inorganic or fatty acid salts as well as the oxy salts thereof can be used in the formation of the metal derivatives.

Typical compounds or condensation products obtained according to the foregoing procedure where wax-phenol (3-16), for example, was used as the initial reactant may be designated as metal phenates of wax-phenol disulfide (3-16); metal phenates of wax-phenol monosulfides (3-16). etc. Where a wax-substituted naphthol is used a the initial reactant, the products may be similarly designated as metal naphtholates of waxnaphthol sulfides.

It will be understood that when a mixture of aliphatic hydrocarbon compounds, such as petroleum wax. for example, is used as the source of the alkyl substituents, the resulting composition will be an intimate mixtureof compounds or sulfides of alkyl-substituted aryl metal oxides (sulfldes of alkyl-substituted aromatic hydroxylates in which the hydroxyl hydrogen is substituted In the with the same metal) which compounds difier from each other with respect to the nature of the alkyl substituent. In other words, where the alkylation of the aryl nucleus ha been effected with a mixture of aliphatic hydrocarbons, the resulting product will likewise be a mixture of com aryl metal oxides which I. have prepared and tested to demonstrate their value as addition agents for viscous mineral oils.

Table I Cobaltous phenate of wax-p n l Aluminum phenate of wax-phenol disulfide (3-16) Sodium phenate, of wax-phenol disulfide (3-16) Calcium phenate of Wax-phenoldisulfide (3-14) Barium phenate f wax-phenol disulfide (3-14) Cobaltous phenate of wax-phenol monosulflde Stannous naphtholate of wax-phenol disulfide 'It is to be understood that although I have described certain preferred procedures for synthesizing the products contemplated by this invention and have listed a number of'illustrative compounds or condensation products which are typical thereof, the invention is not limited to disulfide (3-16) Stannous phenate of wax-phenol disulfide (3-16) 2. A composition of matter as defined in claim 1 wherein the'metal is selected from the tgioup consisting of cobalt, tin, aluminum, barium, calcium, and sodium. I

3. As a new compositlonoi matter, a metal salt of an alkylated phenol sulfide having the general formula in which R and R represent aliphatic hydrocarbon groups containing at least twenty carbon atoms; a: is selected from the integers 1, 2, and 3; M represents the hydrogen equivalent of a metal; and n is selected from the integers lto 4.

4. As a composition of matterfan intimate mixture of oil-miscible metal salts of alkylated hydroxyaromatic sulfide compounds wherein the hydroxyl hydrogen atoms of said compounds are substituted with the same metal; the alkyllsubstituents in said compoundsare attached to the aryl nuclei and. consist of aliphatic hydrocarbon radicals containing at least 20 carbon atoms and corresponding substantially to the different aliphatic hydrocarbons contained in paraflln wax;

and each of said compounds is characterized by atleast twoof the substituted aryl nuclei which are interconnected by at least one atom oi. sulfur. 5. A composition of matter as defined in claim 1 in which the metal is calcium.

6. A composition of matter as defined in c1aim- 1 in which the metal is barium.

7. A composition of matter as defined in claim 1 in which the metal is tin.

the particular procedures or products but includes Within its scope such changes andmodifications as fairly come within the spirit of the appended claims.

Iclaim: 1. As a new composition of matter, an oilmiscible condensation product of a wax-substituted aryl metal oxide in which the oxygen of the metal oxide group is directly attached to the aryl nucleus and in which at least two waxsubstituted aryl nuclei are interconnected by at least one-atom of sulfur.

8. A composition of matter as defined in claim 3 wherein the metal is selected from the group consisting of cobalt, tin, aluminum, barium, calcium and sodium. r

9. Acomposition of matter as defined in claim 3 in which the metal is calcium.

10. A composition of matter as defined in claim 3 in which the metal is barium.

11. A composition of matter as defined in claim 3 in which the metal is tin.

ORLAND M. REIFF. 

